WO1997010172A1 - Procede et dispositif pour separer de l'hydrogene d'un melange gazeux - Google Patents

Procede et dispositif pour separer de l'hydrogene d'un melange gazeux Download PDF

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Publication number
WO1997010172A1
WO1997010172A1 PCT/DE1996/001669 DE9601669W WO9710172A1 WO 1997010172 A1 WO1997010172 A1 WO 1997010172A1 DE 9601669 W DE9601669 W DE 9601669W WO 9710172 A1 WO9710172 A1 WO 9710172A1
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Prior art keywords
hydrogen
gas mixture
oxygen
water
binding
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PCT/DE1996/001669
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German (de)
English (en)
Inventor
Helmut Rehm
Klaus Weller
Peter Schoenfeld
Original Assignee
Siemens Aktiengesellschaft
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Priority to JP9511555A priority Critical patent/JPH11513348A/ja
Priority to EP96938923A priority patent/EP0850191A1/fr
Publication of WO1997010172A1 publication Critical patent/WO1997010172A1/fr

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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K9/00—Arrangements for cooling or ventilating
    • H02K9/26—Structural association of machines with devices for cleaning or drying cooling medium, e.g. with filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/265—Drying gases or vapours by refrigeration (condensation)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/266—Drying gases or vapours by filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/104—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/108—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/80—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/402—Further details for adsorption processes and devices using two beds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0405—Purification by membrane separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042—Purification by adsorption on solids
    • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435—Catalytic purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0495—Composition of the impurity the impurity being water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a method and a device for separating hydrogen from a gas mixture which contains hydrogen, oxygen and a remainder and is produced on an electrical machine, in particular a turbogenerator filled with hydrogen.
  • a reprocessing of contaminated hydrogen which accumulates on seals and the like of an electrical machine, is becoming increasingly interesting.
  • a reprocessing of contaminated hydrogen, where impurities can be air components as well as oil vapors and the like from lubricants and sealants, can significantly limit a loss of hydrogen and thus, in addition to facilitating conditions for the correct monitoring of the hydrogen inventory, can contribute to a welcome reduction in the operating costs of the electrical machine.
  • a method and a device for the disposal of exhaust gas, which contains hydrogen and a residual gas, from an electrical machine filled with hydrogen, are described in WO 94/10740 A1.
  • the hydrogen is separated from the residual gas in that the residual gas is separated from the exhaust gas and is returned to the electrical machine.
  • the residual gas is separated, for example, by the residual gas being taken up by a solid matrix.
  • the device for disposal of the exhaust gas is connected, for example, to a sealing oil container in which special oil, which is used to seal the electrical machine and saturates with hydrogen during operation, is collected.
  • the hydrogen and the residual gas are extracted from the sealing oil by vacuum extraction, and the hydrogen is returned to the electrical machine after separation of the residual gas.
  • WO 94/10739 AI relates to the discharge of hydrogen from an electric machine filled with hydrogen.
  • the primary aim is to completely remove the hydrogen from the electrical machine so that it can be opened for a revision or repair purpose.
  • the hydrogen is taken up by a solid-state store, in particular a hydride store, which stores the hydrogen in the form of certain metal hydrides.
  • the object of the invention is to provide a method for separating hydrogen from a gas mixture which contains hydrogen, oxygen and a remainder, which gas mixture on an electrical machine.
  • a corresponding device should also be specified.
  • the method according to the invention for solving this problem for separating hydrogen from a gas mixture which contains hydrogen, oxygen and a residue and is produced on an electrical machine comprises the following steps: a) binding the oxygen to the hydrogen in the gas mixture ⁇ mixed to form water; b) separating the water from the gas mixture; and c) separating the hydrogen from the gas mixture by binding the hydrogen in a solid state reactor.
  • An essential advantage of this method is that neither extreme temperatures nor extreme pressures or unusual and difficult to manipulate materials are required. Only widely used materials and measures are used.
  • the binding of the oxygen to the hydrogen is preferably carried out catalytically, that is to say by means of an appropriate catalyst.
  • a catalyst can consist wholly or partly of metals such as platinum and palladium or of certain metal oxides; further information can be found in the book "Ullmann's Encyclopedia of Industrial Chemistry” cited above.
  • the gas mixture before the step of binding the oxygen to the hydrogen
  • the additional admixing of the hydrogen preferably increases a concentration of the hydrogen in the gas mixture in such a way that ignition of the gas mixture is impossible.
  • it is preferred to use as the additionally admixed hydrogen such hydrogen which was previously separated from the gas mixture. A certain cycle of hydrogen is thus formed, which circulates for the purpose of lowering the flammability of the gas mixture and thus avoids having to provide additional hydrogen.
  • a conventional heat exchanger can be provided which, by cooling the gas mixture after binding the oxygen to the hydrogen, brings about the desired condensation; in addition, preferably additionally, the water-containing mixture can be subjected to centrifugal separation, for example in a cyclone.
  • molecular sieving of the gas mixture is preferably carried out.
  • This molecular sieving can be carried out by passing the gas mixture through a special zeolite, a so-called molecular sieve.
  • This molecular sieving is preferably carried out in an arrangement of two molecular sieves, the molecular sieving of the gas mixture taking place in one of the molecular sieves and another molecular sieve being regenerated by flushing with dry gas, preferably hydrogen.
  • dry gas preferably hydrogen
  • the dry gas that is used to regenerate a molecular sieve is preferably water substance which was previously separated from the gas mixture and which is fed back into the gas mixture before the step of separating the water takes place.
  • the water accumulated in a molecular sieve is fed in this way to the or newly provided gas mixture before the gas mixture, which is present anyway, is removed from it. It is sensible for a molecular sieve to be preceded by a water separator which operates in some other way, be it a cyclone or a condenser, and it is this water separator which ultimately absorbs the water collected in the molecular sieve and leads to disposal.
  • water removed from the gas mixture is saturated with dissolved hydrogen; depending on the quantities involved, this proportion of hydrogen may be of minor importance and can be accepted, but it is of course also possible to subject this water laden with hydrogen to vacuum extraction or the like before it is finally disposed of in order to dissolve it Remove hydrogen; the resulting, naturally contaminated hydrogen can be returned to the gas mixture to be worked up anyway.
  • the step of separating the water it is preferred in the step of separating the water to reduce a concentration of water in the gas mixture to such an extent that it corresponds to a dew point of at most - 70 ° C. This means that condensation only takes place in the gas mixture when the gas mixture is cooled below a corresponding temperature. Treatment of the gas mixture at a cryogenic temperature is not necessarily associated with this measure.
  • the hydrogen is stored in the solid state reactor in the step of binding to the solid state reactor, and the rest of the gas mixture is removed. Further explanations of suitable storages can be found below.
  • the hydrogen substance is also preferably bound in an arrangement with at least two stores, the binding being carried out in one of the stores and another store giving off hydrogen previously stored. The arrangement can thus ensure an essentially stationary operation of the method.
  • the hydrogen is bound to a membrane in the solid state reactor and diffuses through the membrane; in this way it is separated from the rest of the gas mixture. Further explanations of a solid-state reactor equipped in this way can also be found below.
  • the method of any configuration is particularly suitable for the treatment of a gas mixture which is obtained from a turbogenerator which is filled with hydrogen, and the hydrogen separated from the gas mixture is returned to the electrical machine.
  • a device for separating hydrogen from a gas mixture containing hydrogen, oxygen and a remainder on an electrical machine which device has the following components which the gas mixture can flow through in succession: a) a reactor for binding the oxygen to the hydrogen to form water; b) a water separator for separating the water from the gas mixture; and c) a solid-state reactor for separating the hydrogen by binding the hydrogen in the solid-state reactor.
  • the device preferably has a return line for admixing previously separated hydrogen to the gas mixture upstream of the reactor for binding the oxygen to the hydrogen.
  • the reactor for binding the oxygen to the hydrogen preferably contains a catalyst for catalyzing a reaction between the oxygen and the hydrogen.
  • a catalyst for catalyzing a reaction between the oxygen and the hydrogen is of particular importance in connection with the development just described, in which the ignitability of the gas mixture is reduced by admixing additional hydrogen. In such a case, it is still possible to bring about a slowed down and therefore safe catalyzed reaction due to a high excess of hydrogen. Even without the addition of additional hydrogen, in particular if the content of the hydrogen in the mixture is already high enough or other measures have been taken to prevent unintentional ignition, the provision of a catalyst for binding the oxygen to the hydrogen is necessary advantageous since such a catalyzer initiates the desired reaction automatically and without special additional ignition measures.
  • a compressor in the device in front of the reactor for binding the oxygen to the hydrogen.
  • This compressor can be used to reduce the volume of the gas mixture to be treated and thus to keep the overall dimensions of the device small; it can also be useful in order to obtain a pressure pressure which is favorable for further reactions in the gas mixture. to increase. Attention is drawn to the possibility of completing a last step for separating the hydrogen from the gas mixture by diffusing the hydrogen through a corresponding membrane. In order for this to take place at an appropriately high rate, it is necessary to set a pressure drop of sufficient height above the membrane. The compressor can also be advantageous for this.
  • the water separator in the device preferably comprises a condenser and / or a cyclone.
  • a condenser and a cyclone are well suited for separating water in large quantities. They are therefore particularly suitable in order to be arranged immediately behind the reactor for binding the oxygen to the hydrogen and to remove most of the water which has formed in the gas mixture from the gas stream.
  • a condenser and a cyclone also make it possible to continuously discharge separated water and thus to operate the device continuously and over relatively long periods of time; this is of great importance for use on a large dynamoelectric machine.
  • the water separator furthermore preferably has an arrangement with a molecular sieve in the device.
  • a molecular sieve can serve to reduce the water content to the lowest proportions and, in particular, achieve water contents which correspond to dew points in the range of cryogenic temperatures. This is important in order to be able to obtain hydrogen of the highest purity from the gas mixture.
  • a molecular sieve is less suitable for removing a larger amount of a substance from a gas mixture.
  • a water separating device of another type in particular a condenser or a cyclone, in front of a molecular sieve and / or to create a possibility of being able to replace a molecular sieve which is fully loaded with water by a fresh molecular sieve without interrupting the operation of the device to have to.
  • the device has in particular an arrangement 12
  • the storage capacity for hydrogen is not important in this context. If such a filter is completely loaded with pollutants, it can be replaced. Regeneration of the storage material is generally possible, but it does require heating to a high temperature, which is generally a few hundred degrees Celsius, which is not absolutely feasible when the filter is in the device.
  • FIG. 1 shows a diagram for a device for separating hydrogen from a gas mixture which is assigned to an electrical machine; again when the temperature at the storage tank rises above a certain limit, which is by no means very high. Such a process of storing is reversible; it can be repeated at will.
  • two stores are preferably provided, which can alternatively be connected to a feed line for supplying the gas mixture and to a clean gas line for discharging the separated hydrogen material, so that one of the stores in each case contains the gas mixture can be loaded with hydrogen, while the other store releases previously stored hydrogen.
  • a heat pump is provided with particular preference, which can cool the store provided for the uptake of hydrogen and at the same time heat the store provided for the release of stored hydrogen. Such a heat pump allows the device to be operated particularly economically.
  • a preferred further development of the device of any configuration described above is characterized by an additional filter provided in the gas routing system between the water separator and the solid state reactor, with the possibly present pollutants, including in this connection carbon monoxide and carbon dioxide, possibly still existing oxygen as well as nitrogen and sulfur compounds , can be removed from the gas mixture before it reaches the solid state reactor.
  • An alloy such as can be used for storing hydrogen in the form of a metal hydride, is again suitable as the material for such a filter.
  • Such an alloy is relatively easy Ver ⁇ bonds one with the aforementioned pollutants wa ⁇ their encryption use as material for spoke Was ⁇ er ⁇ toff can be problematic chen ma ⁇ . Of course, this tendency to react can be used to advantage to remove these pollutants from the gas 14
  • a reactor 6 then arrives, which causes the oxygen in the gas mixture to be bound to the hydrogen to form water.
  • the reactor 6 preferably contains a corresponding catalyst, which can be platinum or palladium, for example. Certain metal oxides are also suitable for the catalyst. Depending on the type of catalyst, it may be appropriate to make the reactor 6 heatable in order to be able to reach an operating temperature which is favorable for the catalyst.
  • the gas mixture leaving the reactor 6 flows to a water separator 7, 8, 9 and there first to a cooler 7.
  • This cooler 7 can be equipped as a condenser, i.e. it can cool the gas mixture to such an extent that a substantial proportion of the water contained in it condenses.
  • Downstream of the cooler 7 is a cyclone 8, which separates water which is dispersed in the form of mist in the gas mixture. In the cyclones 8, a condensation of water which is in
  • a molecular sieve 9 contains, for example, an essential component, a zeolite, which is able to filter out individual water molecules from the gas mixture.
  • a zeolite is, for example, a relatively complex compound composed of silicon, aluminum, oxygen and sodium; corresponding substances are known.
  • a correspondingly provided valve arrangement makes it possible to alternatively let the gas mixture flow through the molecular sieves 9 or to expose it to a flow of dry gas which absorbs and carries away the water stored in a molecular sieve 9.
  • FIG. 1 shows an electrical machine 1 filled with water material with a shaft seal 2, which seals the passage of a shaft protruding from the electrical machine 1 through a housing of this machine 1. This is done with special oil, which becomes saturated with hydrogen in the course of its use and from which the water has to be removed again in order to ensure proper functioning. This takes place in a degassing container 3, preferably by vacuum extraction or a similar treatment.
  • oil which is used to seal an electrical machine 1
  • oil which is used to seal an electrical machine 1
  • gases especially components of the air and therefore oxygen, as well as other gases, hereinafter referred to as "rest" become.
  • these other gases are, in particular, nitrogen, which is relatively inert and therefore not necessarily problematic, as well as carbon dioxide and noble gases.
  • Other constituents of the remainder can be hydrocarbons which are contained in the oil or which result from decomposition.
  • the removal of the oxygen and the residue is also important, since these gases could otherwise penetrate into the electrical machine 1 when the oil is returned and could contaminate the hydrogen therein permanently. Since the hydrogen generally has cooling tasks, its function would be significantly impaired by the presence of other gases. Accordingly, oxygen and the rest must be carefully kept away from the machine 1.
  • the gas mixture first arrives at a compressor 5, where it is transferred to a compressor 16
  • FIG. 1 shows the two molecular sieves 9 with a valve arrangement, which permits such an arrangement.
  • the hydrogen loaded with water in a molecular sieve 9 can be returned through a purge gas line 15 to the inlet area of the device, in particular in front of the water separator formed by the cooler 7, the cyclones 8 and the molecular sieves 9. This means that no hydrogen is lost and there is no exhaust gas.
  • the water released from the molecular sieve 9 finally collects in liquid form in the cooler 7 or in the cyclones 8 and can be removed therefrom by appropriate means, be it intermittent or continuous.
  • a control device which controls the operation of the device is not shown in FIG.
  • the design of such a control device is known per se and, as the responsibility of the person skilled in the relevant art, does not require any further explanation at this point.
  • the control device is also not shown in the drawing.
  • the additional filter 10 preferably contains hydride storage material, which stores hydrogen in the form of hydrides, as an essential component.
  • the hydride storage material is not used in the additional filter 10 for storing hydrogen, but instead one uses ⁇ its affinity for the accumulation of the pollutants mentioned. If the hydride storage material is completely loaded with such pollutants, then it or the entire additional filter 10 must be replaced. Regeneration is possible in some cases, but it requires the hydride storage material to be heated to temperatures of a few hundred degrees Celsius, so that this preferably takes place outside the device.
  • the gas mixture arrives at a solid-state reactor 11, which removes all remaining residues from the gas mixture and provides the hydrogen in the highest purity.
  • An exhaust pipe 12 serves to discharge the residues remaining from the gas mixture; the pure hydrogen is returned to the electrical machine 1 through a clean gas line 13.
  • FIG. 2 shows a preferred exemplary embodiment of the solid-state reactor 11.
  • Essential components of this solid-state reactor 11 are two hydride stores 17, which are connected to the exhaust gas line 12, the clean gas line 13 and the supply line 16 (see FIG. 1) via corresponding valves 18 and 19 .
  • the connections to the exhaust gas line 12 are made via pressure relief valves 18, through which the residues separated from the gas mixture escape when the pressure in a hydride reservoir 17 exceeds a certain threshold. More complex valve arrangements are of course possible, but not absolutely necessary.
  • Switching valves 19 finally make it possible to alternatively connect the hydride accumulators 17 to the feed line 16 or the clean gas line 13.
  • Two hydride stores 17 are provided in order to permit quasi-continuous operation.
  • One of the hybrid stores 17 is connected to the feed line 16 and another of the hybrid stores 17 is connected to the clean gas line 13.
  • Each hydride storage device 17 has a water jacket 20, with the aid of which it is optionally cooled or warmed up by a heat pump 21, again via corresponding switching valves. So that a hydride reservoir 17 binds hydrogen, it is cooled, and for this purpose cold water is pumped into its water jacket via a cold water pump 22 and correspondingly connected valves. If a hydride store 17 is to release stored hydrogen again, its water jacket 20 is filled with warm water via the hot water pump 23 and the stored hydrogen is released, so that it can get into the clean gas line 13.
  • the solid-state reactor 11 with hybrid accumulators 17 and the heat pump 21 looks complex at first glance, but depending on the size of the hydride accumulators 17, it may also allow the storage of all the hydrogen contained in the electrical machine 1 when it is being revised - or for repair purposes. See also the corresponding documents of the cited prior art.
  • the cooler described with reference to FIG. 1 can be used to operate the heat pump 21 conventional separator, which removes water and oil vapors that can occur in the sealing system in a conventional manner.
  • the gas mixture then arrives in a device of the type described above. In the reactor 7, the oxygen present is bound to the hydrogen and water is formed. After the reactor, the gas mixture contains 90% hydrogen, 0.05% oxygen, 7% nitrogen and 2.35% water.
  • This gas mixture arrives at the water separator 7, 8, 9 and finally at the molecular sieve 9.
  • the gas mixture obtained behind the molecular sieve 9 contains 92% water, 0.05% oxygen, 7% nitrogen and 0.05% water. In this form, it arrives at the solid-state reactor 11, in which further purification takes place and where a clean gas is finally obtained, which consists of 99.999% hydrogen and the only essential impurities are 0.0001% oxygen, 0.0005% nitrogen and 0.0004% water. This clean gas is returned to the electrical machine 1.
  • the hydrogen is present in the electrical machine 1 with a purity of only about 97%.
  • hydrogen with a considerably higher purity, namely 99.999% is obtained and returned to the electrical machine 1, and thereby the proportions of other gases in the electrical machine are reduced.
  • a desired purity of the hydrogen substance can be set in the electrical machine 1.
  • the amount of gas mixture treated in the device is 1 NM3 / h; the total amount of gas conveyed in the device, which includes the hydrogen circulating as mentioned, is about 3.5 NM3 / h. 20th
  • FIG. 3 shows another preferred exemplary embodiment for the solid-state reactor 11, an essential component being a membrane housing 25 with a hydrogen-permeable membrane 26 arranged therein.
  • the membrane 26 encloses a space into which only hydrogen can get, which is embedded in the membrane 26 and diffuses through it. Outside of this space, the feed line 16 opens into the membrane housing 25 and supplies the pre-cleaned gas mixture. Only the hydrogen can diffuse through the membrane 26 and thus reach the clean gas line 13; Oxygen and other components of the gas mixture cannot pass through the membrane 26; They accumulate in the membrane housing 25 outside the space closed by the membrane 26 and can reach the exhaust pipe 12 through a pressure relief valve 27.
  • a nitrogen supply 28 is provided, from which pure nitrogen can be let into the membrane housing 25 if necessary, for example for purging.
  • a corresponding shut-off valve 29 is provided in the feed line 16.
  • An elevated temperature may be advantageous for operating the membrane 26; if necessary, a heater 30 can be provided for this.
  • Materials for the membrane 26 are known in the prior art; Materials such as palladium and nickel and, in addition, certain plastics which are permeable to hydrogen come into question. An example of such a plastic is the aromatic polyimide marketed under the trade name "Naphion".
  • the solid-state reactor 11 according to FIG. 3 has a simpler structure than the solid-state reactor 11 according to FIG. 2; However, this design-related relative advantage is offset by a function-related relative disadvantage. To one 22

Abstract

L'invention concerne un procédé et un dispositif permettant de séparer de l'hydrogène d'un mélange gazeux contenant de l'hydrogène, de l'oxygène et un reste, et provenant d'une machine électrique (1). L'oxygène est tout d'abord lié à l'hydrogène pour former de l'eau, l'eau est séparée, puis l'hydrogène est séparé par liaison dans un réacteur à solides (11). Le dispositif qui permet de mettre ledit procédé en ÷uvre, comprend un réacteur (6) pour lier l'oxygène à l'hydrogène, un séparateur d'eau (7, 8, 9) pour séparer l'eau, ainsi qu'un réacteur à solides (11). Ce procédé et ce dispositif conviennent particulièrement bien au traitement d'un mélange gazeux provenant d'un turbo-alternateur refroidi par eau.
PCT/DE1996/001669 1995-09-14 1996-09-05 Procede et dispositif pour separer de l'hydrogene d'un melange gazeux WO1997010172A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP9511555A JPH11513348A (ja) 1995-09-14 1996-09-05 気体混合物から水素を分離するための方法および装置
EP96938923A EP0850191A1 (fr) 1995-09-14 1996-09-05 Procede et dispositif pour separer de l'hydrogene d'un melange gazeux

Applications Claiming Priority (2)

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DE19534095A DE19534095A1 (de) 1995-09-14 1995-09-14 Verfahren und Vorrichtung zum Abscheiden von Wasserstoff aus einem Gasgemisch
DE19534095.7 1995-09-14

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WO1997010172A1 true WO1997010172A1 (fr) 1997-03-20

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JP (1) JPH11513348A (fr)
KR (1) KR19990044627A (fr)
CN (1) CN1196030A (fr)
CZ (1) CZ76598A3 (fr)
DE (1) DE19534095A1 (fr)
HU (1) HUP9900740A2 (fr)
WO (1) WO1997010172A1 (fr)

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JP2002543033A (ja) * 1999-05-03 2002-12-17 ヌーベラ ヒューエル セルズ 一体化されたシフト床、優先酸化反応装置、補助反応装置及び装置制御機構を有する自己熱交換式改質装置
US10882742B2 (en) 2016-02-02 2021-01-05 Sabic Global Technologies B.V. Process for separation of hydrogen and oxygen
US10947115B2 (en) 2015-11-25 2021-03-16 Sabic Global Technologies B.V. Process for separation of hydrogen and oxygen

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EP1580868A1 (fr) * 2004-03-23 2005-09-28 Siemens Aktiengesellschaft Alternateur refroidi par hydrogène avec un filtre utilisant une membrane
CN108212163B (zh) * 2018-01-27 2020-09-04 西北有色金属研究院 一种氢分离用Ni基复合膜管及其制备方法
CN110980647B (zh) * 2019-12-25 2021-04-06 厦门市乐立润安科技有限公司 一种适用于液化过程的氢气净化方法
CN111591958A (zh) * 2020-05-22 2020-08-28 力行氢能科技股份有限公司 氢气提纯设备
CN111453699B (zh) * 2020-05-22 2021-08-31 力行氢能科技股份有限公司 一种制氢及氢气提纯装置

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JP2002543033A (ja) * 1999-05-03 2002-12-17 ヌーベラ ヒューエル セルズ 一体化されたシフト床、優先酸化反応装置、補助反応装置及び装置制御機構を有する自己熱交換式改質装置
US10947115B2 (en) 2015-11-25 2021-03-16 Sabic Global Technologies B.V. Process for separation of hydrogen and oxygen
US10882742B2 (en) 2016-02-02 2021-01-05 Sabic Global Technologies B.V. Process for separation of hydrogen and oxygen

Also Published As

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CZ76598A3 (cs) 1998-07-15
JPH11513348A (ja) 1999-11-16
EP0850191A1 (fr) 1998-07-01
DE19534095A1 (de) 1997-03-27
CN1196030A (zh) 1998-10-14
KR19990044627A (ko) 1999-06-25
HUP9900740A2 (hu) 1999-07-28

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